CN109923689B - Method for purifying organic substance used as material of organic light-emitting element - Google Patents
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K99/00—Subject matter not provided for in other groups of this subclass
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/311—Purifying organic semiconductor materials
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- Electroluminescent Light Sources (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a method for purifying an organic substance used as a material for an organic light-emitting element, which can provide a high-purity organic substance in a simple and efficient manner, and particularly, can provide a high-purity organic substance which can improve production efficiency by increasing the process progress rate by suppressing outgassing, and can prevent defects due to uneven vapor deposition by stabilizing the vapor deposition rate.
Description
Technical Field
Cross reference to related applications
The present application claims priority based on korean patent application No. 10-2017-0121474, year 9, month 20, 2017, the entire contents of which are incorporated herein by reference.
The present invention relates to a method for purifying an organic substance used as a material for an organic light-emitting device.
Background
As examples of the use of organic materials for electronic devices such as organic light-emitting devices, organic semiconductor devices, organic photoelectric conversion devices, and organic sensor devices have increased, it has become important to provide high-quality organic substances at low cost, which are used as materials for manufacturing organic electronic devices.
In particular, when the conductive organic substance used for the electron injection layer, the electron transport layer, the hole injection layer, the hole transport layer, the light emitting layer, the cover layer, and the like of the organic light emitting device contains impurities, the performance of the organic electronic device may be seriously adversely affected, and therefore, a purification process with a high purity of preferably 99.9% or more is required.
In addition, there is a trend in recent years to develop a process for recovering and purifying conductive organic substances used for the production of organic electronic devices. For example, an organic light-emitting element is manufactured by evaporating a conductive organic material in a vacuum state to deposit the conductive organic material on a substrate, and in this case, the amount of the conductive organic material deposited on the substrate is less than 10% of the amount of the organic material evaporated, and the remainder is adhered to the surface of a process apparatus. In this case, even if the conductive organic substance adhering to the surface of the process apparatus is recovered by scraping or the like, various impurities are contained therein, and therefore, a process of re-purification with high purity is required for reuse thereof.
Conventionally, sublimation purification is used as a method for purifying a large amount of a high-purity conductive organic substance used for manufacturing an organic electronic device such as an organic light-emitting device at a practical level. The sublimation purification method is a purification method utilizing a difference in sublimation point between a conductive organic substance and impurities contained therein, and specifically includes the following steps: the conductive organic substance disposed at one end in the longitudinal direction of the interior of the tube maintained in a vacuum state is heated to a sublimation point or higher and sublimated, and the conductive organic substance is cooled at the other end in the longitudinal direction of the interior of the tube and recrystallized, thereby obtaining a high-purity conductive organic substance from which impurities are removed. However, according to the sublimation purification method, the purified organic material recrystallized and deposited on the inner wall of the tube is scraped by hand and collected, and in this case, the organic material is exposed to the air and may be contaminated or deteriorated during the scraping process by detaching the outer tube.
In particular, when an organic substance containing such impurities is used as a material of an organic light-emitting element to manufacture the organic light-emitting element, the process preparation time is increased due to Out-gassing (Out-gassing) generated in the vacuum deposition process, which causes a problem of lowering the production efficiency, and the deposition rate becomes unstable, which causes unevenness in luminance to occur in a portion deposited with an uneven thickness, which causes a problem of a failure.
Disclosure of Invention
The purpose of the present invention is to provide a method for purifying an organic substance used as a material for an organic light-emitting element, which can obtain a high-purity organic substance by a simple and effective purification method.
According to an embodiment of the present invention, there is provided a method of purifying an organic substance used as a material of an organic light-emitting element, including: a step of purifying an organic substance used as a material of the organic light-emitting element by sublimation; a step of melting the sublimated and purified organic substance to obtain a coagulated organic substance; and a step of separating and recovering the condensed organic substances from the impurities.
In general, since an organic substance used for an organic light-emitting element should be in a high-purity state with a very small impurity content, it is difficult to obtain a substance having a desired purity only by a sublimation purification step.
However, the method for purifying an organic substance used as a material of an organic light-emitting element according to the present invention is based on the following method: a method for removing impurities from a substance to be purified by causing phase equilibrium to occur when a sublimed purified organic substance is melted. Thus, when the sublimated and purified organic substance is melted, the high-purity organic substance is separated from the impurities and condensed, and the high-purity organic substance can be obtained through a process of cooling and recovering the high-purity organic substance. When such a high-purity organic substance is used as a material of an organic light-emitting element, the production efficiency can be improved by increasing the process progress speed by suppressing outgassing (Out scattering), and defects due to uneven vapor deposition can be prevented by stabilizing the vapor deposition speed.
Next, a method for purifying an organic substance used as a material of an organic light-emitting element according to an embodiment of the present invention will be described in more detail.
A method of purifying an organic substance used as a material of an organic light emitting element according to an embodiment of the present invention may include a step of measuring a melting temperature (Tm) and a 1% thermal decomposition temperature (Td 1%) of the organic substance. The melting temperature can be measured by DSC (Differential scanning calorimetry). The 1% thermal decomposition temperature is a temperature at which the initial weight of the organic substance is reduced by 1%, and can be measured by TGA (Thermogravimetric analysis).
The method for purifying an organic substance includes a step of purifying an organic substance used as a material of an organic light-emitting element by sublimation. Separation by chromatography or recrystallization is difficult due to similarity in polarity between different substances of a mixture, but when the difference in Melting temperature (Tm; Melting Point) between an organic substance and an impurity is large, or when the difference in sublimation temperature is large without the above-mentioned Melting temperature, a desired substance can be purified by such a sublimation purification step.
Specifically, the sublimation purification step is described below. First, the cartridge containing the organic substance is disposed in the inner tube, and the inner tube can be evacuated. The inner tube may be controlled to about 10 deg.f by a vacuum pump-5Vacuum state of the tray. In this case, although the vacuum Pump may be configured differently depending on the device characteristics, a Dry Pump (Dry Pump) and a TMP (Turbo Molecular Pump) may be used together in general. In particular, it may be up to about 10-2Low vacuum of the tray uses a dry pump, then, up to about 10-5TMP was used. By performing the sublimation purification step in a vacuum state, the sublimation or vaporization temperature is lowered and the process temperature is lowered, whereby the possibility of thermal damage to the organic substance can be reduced. In addition, low temperature is stable in terms of temperature maintenance as compared with high temperature, and impurities inside the apparatus can be removed.
Then, the temperature may be gradually increased by the heater to form a temperature gradient over the entire inner tube. The faster the temperature rise rate, the more advantageous the reduction of the process time, but when the temperature is raised too quickly, overshoot (overshoot) may occur and the adjustment to a desired temperature may be disadvantageous, and when the temperature exceeds the 1% thermal decomposition temperature measured by the TGA described above, the organic substance may be damaged, so it is preferable to control the temperature rise rate depending on the device and the kind of the organic substance.
When the temperature of the above-mentioned cassette is higher than the sublimation point of the organic substance contained therein, the organic substance starts to sublimate, and after the sublimated gas molecules flow to the outside through the holes of the above-mentioned cassette, they can start to move in the direction in which the vacuum pump is provided, by the pressure gradient. In this case, impurities having a higher sublimation point than the organic substance may remain in the inside of the cartridge, and the moving gas molecules may be converted into a solid phase again in the region of the inner tube having a temperature of less than or equal to the sublimation point, and a crystalline state or an amorphous state may be formed on the inner surface of the inner tube. After a sufficient time, the heating is stopped, the tube is gradually cooled to the same temperature as the normal temperature, the inner tube can be detached, and the purified material formed on the inner surface is scraped and recovered.
However, since a substance used for an organic light-emitting element should be in a high-purity state with a very small impurity content in general, it is difficult to obtain a substance of a desired purity only by a sublimation purification step. Further, when the sublimation purification step is repeated only 2 times or more to obtain a high-purity substance, there are the following problems: a loss of amount occurs in the process of scraping the organic substances from the inner tube, and the organic substances are exposed to the air in the process of detaching the inner tube and the outer tube every time the purification is repeated, a contamination or deterioration phenomenon due to oxygen or water vapor may occur, and the time required for the purification as a whole becomes long.
However, the method for purifying an organic substance used as a material of an organic light emitting element according to an embodiment of the present invention can remove impurities through a process of melting an organic substance purified by sublimation, thereby purifying the organic substance in a simple and efficient manner, and when the organic substance from which impurities are removed through the melting process is used as a material of the organic light emitting element, it is possible to improve production efficiency by increasing a process proceeding speed by suppressing outgassing, stabilize a deposition speed, and prevent a defect due to uneven deposition.
A method of purifying an organic substance used as a material of an organic light-emitting element according to an embodiment of the present invention includes: and a step of recovering the sublimed and purified organic substance, and then melting the organic substance to obtain a coagulated organic substance. When the above sublimed and purified organic substances are melted, phase equilibrium occurs, and the high-purity organic substances are condensed with each other, thereby enabling the removal of impurities from the organic substances intended to be purified. Therefore, a high-purity organic substance can be obtained by the subsequent cooling and recovery step.
The melting step may be performed in a vacuum state of 1 to 10 torr. By performing the melting step in a vacuum state of 10 torr or less, the possibility of thermal damage to the organic substance can be reduced, and low temperature can be kept stable in temperature as compared with high temperature. However, when the above pressure is less than 1 torr, a problem of causing vaporization of the organic substance may occur.
In this case, in order to maintain a constant pressure, an inert gas may be introduced into the apparatus, and the melting may be performed in an inert gas atmosphere. As the inert gas, argon (Ar) gas or nitrogen (N) gas may be used2) And a gas, wherein the higher the purity of the inert gas is, the more reliable the process result can be described.
The melting step may be performed at a temperature of not lower than the melting temperature and lower than the 1% thermal decomposition temperature, and at such a temperature, the melting of the organic substance can be stably performed and the process efficiency can be improved.
The method for purifying an organic substance used as a material of an organic light emitting element according to an embodiment of the present invention may include a step of cooling the organic substance condensed by the melting step. The temperature inside the apparatus can be lowered to room temperature by operating the Fan (Fan) outside the apparatus, and the temperature inside the apparatus can be easily lowered only by controlling the flow rate of the inert gas as high as possible within the range in which the vacuum pressure is maintained.
A method for purifying an organic substance used as a material of an organic light emitting element according to an embodiment of the present invention may include a step of separating and recovering the condensed organic substance from impurities. Thus, high-purity organic substances recovered from impurities can be recovered, and the organic substances can be pulverized and used as materials for organic light-emitting elements. When the pulverized organic substance is used as a material of an organic light-emitting element, the production efficiency can be improved by increasing the process progress speed by suppressing outgassing, and the vapor deposition speed can be stabilized, thereby preventing a problem due to uneven vapor deposition.
In the method of purifying an organic substance used as a material of an organic light emitting element according to an embodiment of the present invention, the above-described purified organic substance may be used as a material of a Capping Layer (CPL).
The purified organic substance may be one whose melting temperature (Tm) can be measured by a differential scanning calorimeter (DSC; differential scanning Calorimetry). Specifically, since the purification method includes a step of melting the organic substance, the organic substance may be an organic substance having a melting temperature. On the other hand, an organic substance whose melting temperature cannot be measured by the DSC, that is, an organic substance that has not a melting temperature and that sublimes directly, cannot be applied to the melting step, and thus there is a problem that impurities cannot be removed efficiently.
In addition, in the method for purifying an organic substance used as a material of an organic light emitting element according to the present invention, the organic substance may be a compound represented by the following chemical formula 1 or 2.
[ chemical formula 1]
[ chemical formula 2]
In the above-described chemical formulas 1 and 2,
R1to R12The same or different from each other, each independently selected from the group consisting of hydrogen, halogen, alkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, aryl group having 6 to 20 carbon atoms and heteroaryl group having 5 to 20 carbon atoms, or R1To R12Are connected with each other to form a ring,
Ar1and Ar2Identical to or different from each other, each independently selected from the group consisting of an aryl group having 6 to 20 carbon atoms and a heteroaryl group having 5 to 20 carbon atoms,
m and n may each independently be an integer of 0 to 4.
R of the above chemical formulas 1 and 21To R12In (b), groups adjacent to each other may form a ring. For example, R of chemical formulas 1 and 21To R8In (b), groups adjacent to each other may combine to form a ring fused with the N-carbazolyl group. R1To R8The ring formed by bonding the groups adjacent to each other is usually a 5-to 8-membered ring, but is preferably a 5-or 6-membered ring, more preferably a 6-membered ring. The ring may be an aromatic ring or a non-aromatic ring, and is preferably an aromatic ring. The aromatic hydrocarbon ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring, but is preferably an aromatic hydrocarbon ring.
In the N-carbazolyl groups of the above chemical formulae 1 and 2, R1To R8Examples of the fused ring bonded to the N-carbazolyl group by any one of the above-mentioned groups include the following.
R of the above chemical formulas 1 and 11To R8In particular, the case where all of the groups are hydrogen atoms (that is, the N-carbazolyl group is unsubstituted), or the case where 1 or more of the groups are any of methyl, phenyl or methoxy groups and the remainder are hydrogen atoms is preferable.
The organic substance may be a compound represented by the following chemical formula 3.
[ chemical formula 3]
In the chemical formula 3 above, the first and second,
X1an N-carbazolyl group substituted or unsubstituted with 1 or more members selected from the group consisting of a halogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms and an aryl group having 6 to 20 carbon atoms; n-thiophenes substituted or unsubstituted with 1 or more members selected from the group consisting of halogens, alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms and aryl groups having 6 to 20 carbon atoms
Oxazinyl (N-
) (ii) a Or an N-phenothiazinyl group which is substituted or unsubstituted with 1 or more members selected from the group consisting of a halogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an aryl group having 6 to 20 carbon atoms
X2An N-carbazolyl group substituted or unsubstituted with 1 or more members selected from the group consisting of a halogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms and an aryl group having 6 to 20 carbon atoms; n-thiophenes substituted or unsubstituted with 1 or more members selected from the group consisting of halogens, alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms and aryl groups having 6 to 20 carbon atoms
An oxazine group; an N-phenothiazinyl group substituted or unsubstituted with 1 or more selected from the group consisting of a halogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an aryl group having 6 to 20 carbon atoms; or-NAr1Ar2，
Ar1And Ar2Each independently an aryl group having 6 to 20 carbon atoms which is substituted or unsubstituted with 1 or more selected from the group consisting of a halogen, an alkyl group, an alkoxy group and an aryl group; or selected from halogen, alkyl, alkoxy and aryl1 or more substituted or unsubstituted heteroaryl groups having 5 to 20 carbon atoms,
B1and B2Are the same or different from each other, each independently hydrogen; deuterium; an alkyl group; an aryl group having 6 to 20 carbon atoms which is substituted or unsubstituted with 1 or more selected from the group consisting of a halogen, an alkyl group, an alkoxy group and an aryl group; a heteroaryl group having 5 to 20 carbon atoms which is substituted or unsubstituted with 1 or more selected from the group consisting of a halogen, an alkyl group, an alkoxy group and an aryl group; or an aralkyl group substituted or unsubstituted with 1 or more selected from the group consisting of halogen, alkyl group, alkoxy group and aryl group,
Z1and Z2May be the same as or different from each other, each independently is hydrogen; deuterium; halogen; an alkyl group; an alkoxy group; an aryl group having 6 to 20 carbon atoms selected from the group consisting of halogen, alkyl, alkoxy and aryl; or a heteroaryl group of 5 to 20 carbon atoms selected from the group consisting of halogen, alkyl, alkoxy and aryl.
X as the above chemical formula 31Substituted or unsubstituted N-carbazolyl, substituted or unsubstituted N-thiophen
Specific examples of the oxazinyl group or the substituted or unsubstituted N-phenothiazinyl group include an N-carbazolyl group, a 2-methyl-N-carbazolyl group, a 3-methyl-N-carbazolyl group, a 4-methyl-N-carbazolyl group, a 3-N-butyl-N-carbazolyl group, a 3-N-hexyl-N-carbazolyl group, a 3-N-octyl-N-carbazolyl group, a 3-N-decyl-N-carbazolyl group, a 3, 6-dimethyl-N-carbazolyl group, a 2-methoxy-N-carbazolyl group, a 3-ethoxy-N-carbazolyl group, a 3-isopropoxy-N-carbazolyl group, a 3-N-butoxy-N-carbazolyl group, a substituted or unsubstituted N-phenothiazinyl group, 3-N-octyloxy-N-carbazolyl, 3-N-decyloxy-N-carbazolyl, 3-phenyl-N-carbazolyl, 3- (4' -methylphenyl) -N-carbazolyl, 3-chloro-N-carbazolyl, N-thiophene
Oxazinyl, N-phenothiazinyl, 2-methyl-N-phenothiazinyl, and the like.
X as the above chemical formula 32Substituted or unsubstituted N-carbazolyl, substituted or unsubstituted N-thiophen
Specific examples of the oxazinyl group and the substituted or unsubstituted N-phenothiazinyl group include X1Examples of the substituted or unsubstituted N-carbazolyl group and the substituted or unsubstituted N-thiophen group
An oxazinyl group, a substituted or unsubstituted N-phenothiazinyl group, and the like.
-NAr of the above chemical formula 31Ar2In Ar1And Ar2Represents a substituted or unsubstituted aryl or heteroaryl group. As Ar above1And Ar2Specific examples of the (B) include phenyl, 1-naphthyl, 2-anthryl, 9-anthryl, 4-quinolyl, 4-pyridyl, 3-pyridyl, 2-pyridyl, 3-furyl, 2-furyl, 3-thienyl, 2-thienyl and 2-
Azolyl, 2-thiazolyl, 2-benzo
Oxazolyl, 2-benzothiazolyl, 2-benzimidazolyl, 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 4-ethylphenyl, 3-ethylphenyl, 2-ethylphenyl, 4-n-propylphenyl, 4-isopropylphenyl, 2-isopropylphenyl, 4-n-butylphenyl, 4-isobutylphenyl, 4-sec-butylphenyl, 2-sec-butylphenyl, 4-tert-butylphenyl, 3-tert-butylphenyl, 2-tert-butylphenyl, 4-n-pentylphenyl, 4-isopentylphenyl, 2-neopentylphenyl, 4-tert-pentylphenyl, 4-n-hexylphenyl, 4- (2' -ethylbutyl) phenyl, 4-n-heptylphenyl, 4-n-octylphenyl, 4- (2' -ethylhexyl) phenyl group, 4-tert-octylphenyl group, 4-n-decylphenyl group, 4-n-dodecylphenyl group, 4-n-tetradecylphenyl group, 4-cyclopentylphenyl group, 4-cyclohexylphenyl group, 4- (4' -methylcyclohexyl) phenyl group, 4- (4' -tert-butylcyclohexyl) phenyl group, 3-cyclohexylphenyl group, 2-cyclohexylphenyl group, 4-ethyl-1-naphthyl group, 6-n-butyl-2-naphthyl group, 2, 4-dimethylphenyl group, 2, 5-dimethylphenyl group, 3, 4-dimethylphenyl group, 3, 5-dimethylphenyl groupPhenyl group, 2, 6-dimethylphenyl group, 2, 4-diethylphenyl group, 2,3, 5-trimethylphenyl group, 2,3, 6-trimethylphenyl group, 3,4, 5-trimethylphenyl group, 2, 6-diethylphenyl group, 2, 5-diisopropylphenyl group, 2, 6-diisobutylphenyl group, 2, 4-di-tert-butylphenyl group, 2, 5-di-tert-butylphenyl group, 4, 6-di-tert-butyl-2-methylphenyl group, 5-tert-butyl-2-methylphenyl group, 4-tert-butyl-2, 6-dimethylphenyl group, 4-methoxyphenyl group, 3-methoxyphenyl group, 2-methoxyphenyl group, 4-ethoxyphenyl group, 3-ethoxyphenyl group, 2-ethoxyphenyl group, 4-n-propoxyphenyl group, 2,3, 5-di-isopropylphenyl group, 2,3, 5-trimethylphenyl group, 2,6, 3-n-propoxyphenyl group, 4-isopropoxyphenyl group, 2-isopropoxyphenyl group, 4-n-butoxyphenyl group, 4-isobutoxyphenyl group, 2-sec-butoxyphenyl group, 4-n-pentyloxyphenyl group, 4-isopentyloxyphenyl group, 2-isopentyloxyphenyl group, 4-neopentyloxyphenyl group, 2-neopentyloxyphenyl group, 4-n-hexyloxyphenyl group, 2- (2' -ethylbutyl) oxyphenyl group, 4-n-octyloxyphenyl group, 4-n-decyloxyphenyl group, 4-n-dodecyloxyphenyl group, 4-n-tetradecyloxyphenyl group, 4-cyclohexyloxyphenyl group, 2-methoxy-1-naphthyl group, 4-n-butyloxy-1-naphthyl group, 2-methoxy-1-naphthyl group, 5-ethoxy-1-naphthyl, 6-methoxy-2-naphthyl, 6-ethoxy-2-naphthyl, 6-n-butoxy-2-naphthyl, 6-n-hexyloxy-2-naphthyl, 7-methoxy-2-naphthyl, 7-n-butoxy-2-naphthyl, 2-methyl-4-methoxyphenyl, 2-methyl-5-methoxyphenyl, 3-ethyl-5-methoxyphenyl, 2-methoxy-4-methylphenyl, 3-methoxy-4-methylphenyl, 2, 4-dimethoxyphenyl, 2, 5-dimethoxyphenyl, 2-methoxy-2-naphthyl, 2-methoxy-4-methylphenyl, 2-methoxy-5-dimethoxyphenyl, 2-methoxy-2-naphthyl, 2-methoxy-2, 2, 6-dimethoxyphenyl group, 3, 4-dimethoxyphenyl group, 3, 5-diethoxyphenyl group, 3, 5-di-n-butoxyphenyl group, 2-methoxy-4-ethoxyphenyl group, 2-methoxy-6-ethoxyphenyl group, 3,4, 5-trimethoxyphenyl group, 4-biphenyl group, 3-biphenyl group, 2-biphenyl group, 4- (4 '-methylphenyl) phenyl group, 4- (3' -methylphenyl) phenyl group, 4- (4 '-methoxyphenyl) phenyl group, 4- (4' -n-butoxyphenyl) phenyl group, 2- (2 '-methoxyphenyl) phenyl group, 4- (4' -chlorophenyl) phenyl group, di-n-butoxyphenyl, 3-methyl-4-biphenyl, 3-methoxy-4-biphenyl, 4-fluorophenyl, 3-fluorophenyl, 2-fluorophenyl, 4-chlorophenyl, 3-chlorophenyl, 2-chlorophenyl, 4-bromophenyl, 2-bromophenyl, 4-chloro-1-naphthyl, 4-chloro-2-naphthyl, 6-methyl-4-biphenyl-bromo-2-naphthyl, 2, 3-difluorophenyl, 2, 4-difluorophenyl, 2, 5-difluorophenyl, 2, 6-difluorophenyl, 3, 4-difluorophenyl, 3, 5-difluorophenyl, 2, 3-dichlorophenyl, 2, 4-dichlorophenyl, 2, 5-dichlorophenyl, 3, 4-dichlorophenyl, 3, 5-dichlorophenyl, 2, 5-dibromophenyl, 2,4, 6-trichlorophenyl, 2, 4-dichloro-1-naphthyl, 1, 6-dichloro-2-naphthyl, 2-fluoro-4-methylphenyl, 2-fluoro-5-methylphenyl, 3-fluoro-2-methylphenyl, 3-fluoro-4-methylphenyl, 2-methyl-4-fluorophenyl group, 2-methyl-5-fluorophenyl group, 3-methyl-4-fluorophenyl group, 2-chloro-4-methylphenyl group, 2-chloro-5-methylphenyl group, 2-chloro-6-methylphenyl group, 2-methyl-3-chlorophenyl group, 2-methyl-4-chlorophenyl group, 3-methyl-4-chlorophenyl group, 2-chloro-4, 6-dimethylphenyl group, 2-methoxy-4-fluorophenyl group, 2-fluoro-4-methoxyphenyl group, 2-fluoro-4-ethoxyphenyl group, 2-fluoro-6-methoxyphenyl group, 3-fluoro-4-ethoxyphenyl group, 2-fluoro-4-fluorophenyl group, 2-methyl-4-chlorophenyl group, 2-methyl-4, 3-chloro-4-methoxyphenyl, 2-methoxy-5-chlorophenyl, 3-methoxy-6-chlorophenyl, 5-chloro-2, 4-dimethoxyphenyl, etc., but is not limited thereto.
In addition, in the present specification, the phrase "substituted or unsubstituted" means that 1 or more substituents selected from deuterium, a halogen group, an alkyl group, an alkenyl group, an alkoxy group, a silyl group, an arylalkenyl group, an aryl group, a heteroaryl group, a carbazolyl group, an arylamine group, a fluorenyl group substituted or unsubstituted with an aryl group, and a nitrile group are substituted or do not have any substituent.
In the present specification, the substituent may be substituted with an additional substituent, and specific examples thereof include a halogen group, an alkyl group, an alkenyl group, an alkoxy group, a silyl group, an arylalkenyl group, an aryl group, a heteroaryl group, a carbazolyl group, an arylamine group, a fluorenyl group substituted or unsubstituted with an aryl group, a nitrile group, and the like, but the substituent is not limited thereto.
According to the method for purifying an organic substance used as a material of an organic light-emitting element of the present invention, a high-purity organic substance can be provided by a simple and effective method, and a high-purity organic substance can be provided in which outgassing is suppressed, a highly reliable process is performed, and defects due to uneven vapor deposition are prevented.
Drawings
Fig. 1 (a) is a photograph of the recovered organic substance after sublimation purification, and (b) is a photograph of the recovered organic substance after melting and cooling.
Fig. 2 is a view schematically showing an apparatus used in the melting and cooling process of the present invention.
Fig. 3 is a graph showing the results of measuring the degree of vacuum of the organic light-emitting devices of example 1 and comparative example 1.
Fig. 4 is a graph showing the results of measuring the vapor deposition rates of the organic light-emitting elements of example 1 and comparative example 1.
Fig. 5 is a photograph (a) of light emission of an element using a material to which a melting process is applied to a cover layer and a photograph (b) of light emission of an element using a material to which a melting process is not applied, among the organic light-emitting elements of example 1 and comparative example 1.
Detailed Description
In the following, preferred embodiments are suggested to aid in understanding the invention. However, the following examples are merely illustrative of the present invention, and the present invention is not limited thereto.
Example 1
1) Purification of organic substance (CPL) as material for cover layer
A melting temperature (Tm) and a 1% thermal decomposition temperature (Td 1%) were measured for a compound represented by the following chemical formula CPL using DSC (Differential scanning calorimeter) and TGA (Thermogravimetric analysis), respectively. Specifically, DSC Q100 v9.6build 290 was used as a DSC device, and Q500 was used as a TGA device. As a result of the measurement, it was confirmed that the melting temperature was approximately 320 ℃ and the 1% thermal decomposition temperature was 382 ℃.
4kg of the above-mentioned compound was charged into the inside of a cartridge of a sublimation purification apparatus and purified by sublimation. Then, the inner tube and the outer tube are detached, and the organic matter crystallized on the wall surface of the inner tube is scraped and recovered. Fig. 1 (a) is a photograph of the organic substance recovered after sublimation purification.
The organic material recovered after sublimation purification is subjected to a melting step using a general sublimation purification apparatus shown in fig. 2. Specifically, 1000g of samples were loaded into 2 quartz boats (quartz boats) each having one side plugged, the plugged portions of the quartz boats were set to the outside in 2 and 3 zones (zones), and the inner tube was controlled to a vacuum state of about 10 torr using a dry pump. At this time, argon gas was introduced into the apparatus to maintain a constant pressure.
Then, zones 2 and 3 were heated to 330 ℃ at a rate of 5 ℃/min. When the sample in each quartz boat was completely melted, the heating was stopped, and the furnace (furnace) was opened to flow argon gas into the inner tube at 300 sccm. The temperature of the furnace is reduced to 50 ℃ by means of an external fan (fan) for cooling. Then, the cooled sample was collected. Fig. 1 (b) is a photograph of the organic matter recovered after melting and cooling. Subsequently, the recovered organic matter was pulverized.
2) Process for producing organic light-emitting element
On a glass substrate, Ag was deposited in a thickness of 100nm, ITO (indium tin oxide) was deposited in a thickness of 100nm, and then the substrate was added to distilled water in which a detergent was dissolved, and washed with ultrasonic waves. After the substrate was washed with nitrogen plasma for 5 minutes, the substrate was transported to a vacuum evaporator. On the ITO transparent electrode thus prepared, a compound represented by the following chemical formula HAT-CN was thermally vacuum-evaporated in a thickness of 5nm to form a hole injection layer. On the hole injection layer, a compound represented by the following chemical formula HTL-1 as a substance transporting holes was vacuum-evaporated at a thickness of 110nm to form a first hole transport layer. Next, a compound represented by the following chemical formula HTL-2, which is another substance that transports holes, was vacuum-evaporated at a thickness of 25nm on the first hole transport layer to form a second hole transport layer. Next, a compound represented by the following chemical formula BH and a compound represented by the following chemical formula BD were vacuum-evaporated at a weight ratio of 19:1 on the second hole transport layer to a film thickness of 20nm to form a light emitting layer. Next, a compound represented by the following chemical formula ETL was vacuum-deposited on the light-emitting layer, and an electron-transporting layer was formed with a thickness of 30 nm. On the electron transport layer, a cathode was formed by vacuum vapor deposition of lithium fluoride (LiF) in a thickness of 1nm, magnesium (Mg) and silver (Ag) in a weight ratio of 10:1, and in a thickness of 12nm in this order. On the cathode, the purified Compound (CPL) was vacuum-evaporated to a thickness of 60nm to form a coating layer.
In the above process, the deposition rate of organic substances other than the luminescent dopant, silver (Ag) and lithium fluoride is maintained
Luminescent dopant and process for producing the same
Co-evaporation with the host material to adjust to the doping concentration. Maintenance of the deposition rate of lithium fluoride on the cathode
Magnesium (Mg) and silver (Ag) respectively
And
co-evaporation at a vacuum degree of 2X 10 during evaporation-7To 5X 10-6And (4) supporting to manufacture the organic light-emitting element.
Comparative example 1
An organic light-emitting element was produced by performing the CPL purification step and the organic light-emitting element production step in the same manner as in example 1, except that the melting step was not performed.
Evaluation of
1) Measurement of vacuum degree
The degree of vacuum of the organic light emitting elements of example 1 and comparative example 1 was measured using a Convectron gauge (Convectron gauge) and an Ionization gauge (Ionization gauge) from Granville Phillips, and the results are shown in fig. 3.
As can be seen from fig. 3, the vacuum degree in example 1 was lower than that in comparative example 1. Thus, it was confirmed that comparative example 1, in which the melting step was not performed, generated outgas (Out bubbling) during the vacuum deposition process and had a high overall vacuum degree.
2) Evaluation of stability of deposition Rate
The vapor deposition rate and the film thickness of the organic light-emitting elements of example 1 and comparative example 1 were measured using IC6 manufactured by Inficon corporation, and the vapor deposition rate was shown in fig. 4.
As is clear from fig. 4, the vapor deposition rate in example 1 is stable as compared with comparative example 1, and comparative example 1 requires a long time of 700 seconds or longer for the stabilization of the vapor deposition rate.
3) Evaluation of appearance of coating layer
In the organic light emitting elements of example 1 and comparative example 1, the appearance of the cover layer was photographed and shown in (a) and (b) of fig. 5. Fig. 5 (a) is a photograph of the appearance of the coating layer of example 1, and it was confirmed that there was no defect such as dark spots or unevenness. On the contrary, fig. 5 (b) is a photograph of the appearance of the coating layer of comparative example 1, and it is confirmed from the figure that the coating layer is partially evaporated in a non-uniform thickness due to the speed fluctuation, thereby generating defects such as dark spots or unevenness.
Claims (11)
1. A method for purifying an organic substance used as a material for an organic light-emitting element, comprising:
a step of purifying an organic substance used as a material of the organic light-emitting element by sublimation;
a step of melting the sublimated and purified organic substance to obtain a coagulated organic substance; and
a step of separating and recovering the condensed organic matter from impurities.
2. The method for purifying an organic substance used as a material of an organic light-emitting element according to claim 1, wherein the organic substance is used as a material of a cover layer.
3. The method for purifying an organic substance used as a material of an organic light-emitting element according to claim 1, wherein the organic substance is a compound represented by the following chemical formula 1 or 2:
chemical formula 1
Chemical formula 2
In the chemical formulas 1 and 2,
R1to R12The same or different from each other, each independently selected from the group consisting of hydrogen, halogen, alkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, aryl group having 6 to 20 carbon atoms and heteroaryl group having 5 to 20 carbon atoms, or R1To R12Are connected with each other to form a ring,
Ar1and Ar2Identical to or different from each other, each independently selected from the group consisting of an aryl group having 6 to 20 carbon atoms and a heteroaryl group having 5 to 20 carbon atoms,
m and n are each independently an integer of 0 to 4.
4. The method for purifying an organic substance used as a material of an organic light-emitting element according to claim 1, wherein the organic substance is a compound represented by the following chemical formula 3:
chemical formula 3
In the chemical formula 3, the first and second organic solvents,
X1is an N-carbazolyl group substituted or unsubstituted with 1 or more members selected from the group consisting of a halogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms and an aryl group having 6 to 20 carbon atoms(ii) a N-thiophenes substituted or unsubstituted with 1 or more members selected from the group consisting of halogens, alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms and aryl groups having 6 to 20 carbon atoms
An oxazine group; or an N-phenothiazinyl group which is substituted or unsubstituted with 1 or more selected from the group consisting of a halogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an aryl group having 6 to 20 carbon atoms,
X2an N-carbazolyl group substituted or unsubstituted with 1 or more members selected from the group consisting of a halogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms and an aryl group having 6 to 20 carbon atoms; n-thiophenes substituted or unsubstituted with 1 or more members selected from the group consisting of halogens, alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms and aryl groups having 6 to 20 carbon atoms
An oxazine group; an N-phenothiazinyl group substituted or unsubstituted with 1 or more selected from the group consisting of a halogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an aryl group having 6 to 20 carbon atoms; or-NAr1Ar2，
Ar1And Ar2Each independently an aryl group having 6 to 20 carbon atoms which is substituted or unsubstituted with 1 or more selected from the group consisting of a halogen, an alkyl group, an alkoxy group and an aryl group; or a heteroaryl group of 5 to 20 carbon atoms substituted or unsubstituted with 1 or more selected from the group consisting of a halogen, an alkyl group, an alkoxy group and an aryl group,
B1and B2Are the same or different from each other, each independently hydrogen; deuterium; an alkyl group; an aryl group having 6 to 20 carbon atoms which is substituted or unsubstituted with 1 or more selected from the group consisting of a halogen, an alkyl group, an alkoxy group and an aryl group; a heteroaryl group having 5 to 20 carbon atoms which is substituted or unsubstituted with 1 or more selected from the group consisting of a halogen, an alkyl group, an alkoxy group and an aryl group; or an aralkyl group substituted or unsubstituted with 1 or more selected from the group consisting of halogen, alkyl group, alkoxy group and aryl group,
Z1and Z2Are the same or different from each other and are independent of each otherGround is hydrogen; deuterium; halogen; an alkyl group; an alkoxy group; an aryl group having 6 to 20 carbon atoms selected from the group consisting of halogen, alkyl, alkoxy and aryl; or a heteroaryl group of 5 to 20 carbon atoms selected from the group consisting of halogen, alkyl, alkoxy and aryl.
5. The method for purifying an organic substance used as a material for an organic light-emitting element according to claim 1, wherein the organic substance is a substance whose melting temperature (Tm) is measurable by a differential scanning calorimeter.
6. The method for purifying an organic substance used as a material of an organic light-emitting element according to claim 1, further comprising a step of measuring a melting temperature (Tm) and a 1% thermal decomposition temperature (Td 1%) of the organic substance before the sublimation purification step.
7. The method for purifying an organic substance used as a material of an organic light-emitting element according to claim 6, wherein the melting is performed at a temperature of not less than the melting temperature but less than the 1% thermal decomposition temperature.
8. The method for purifying an organic substance used as a material of an organic light-emitting element according to claim 1, wherein the melting is performed at a pressure of 1 to 10 torr.
9. The method for purifying an organic substance used as a material of an organic light-emitting element according to claim 1, wherein the melting is performed in an inert gas atmosphere.
10. The method for purifying an organic substance used as a material for an organic light-emitting element according to claim 1, further comprising a step of cooling the condensed organic substance.
11. The method of purifying an organic substance used as a material of an organic light-emitting element according to claim 1, further comprising a step of pulverizing the organic substance separated and recovered from the impurities.
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| KR102555961B1 (en) * | 2022-11-04 | 2023-07-14 | 덕산네오룩스 주식회사 | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof |
| KR20240094052A (en) * | 2022-11-17 | 2024-06-25 | 덕산네오룩스 주식회사 | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100852113B1 (en) * | 2006-11-08 | 2008-08-13 | 삼성에스디아이 주식회사 | Sublimation purification apparatus of organic light-emitting material and the material prepared by using the apparatus |
| CN102924207A (en) * | 2011-08-13 | 2013-02-13 | 广东阿格蕾雅光电材料有限公司 | Organic micromolecule sublimation purifying method |
| WO2013065626A1 (en) * | 2011-10-31 | 2013-05-10 | 出光興産株式会社 | Apparatus for purifying organic material and method for purifying organic material |
| KR20130076272A (en) * | 2011-12-28 | 2013-07-08 | 주식회사 두산 | Organic compound purifying apparatus |
| KR101288441B1 (en) * | 2013-02-20 | 2013-07-26 | 오강현 | Heater for sublimation refinement and method for forming the same |
| JP2013209352A (en) * | 2012-03-30 | 2013-10-10 | Idemitsu Kosan Co Ltd | Organic-material refining device |
| KR20160059609A (en) * | 2014-11-19 | 2016-05-27 | 덕산네오룩스 주식회사 | Display device using a composition for organic electronic element, and an organic electronic element thereof |
| CN106474760A (en) * | 2016-06-01 | 2017-03-08 | 陕西莱特迈思光电材料有限公司 | Organic matter sublimation purification device |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100959824B1 (en) * | 2001-12-15 | 2010-05-28 | 에스케이씨 주식회사 | Apparatus and method for purifying and organic electroluminescent material |
| JP2007230951A (en) * | 2006-03-02 | 2007-09-13 | Canon Inc | Silyl compound, luminescent material and organic electroluminescent element using the same |
| JP5244932B2 (en) * | 2011-03-03 | 2013-07-24 | 株式会社半導体エネルギー研究所 | Organic compound purification method, film formation method, or light emitting device manufacturing method |
| KR101600661B1 (en) * | 2013-05-13 | 2016-03-07 | 제일모직주식회사 | Apparatus for purifying organicelectroluminescent material and method for purifying organicelectroluminescent material |
| KR101289792B1 (en) * | 2013-06-19 | 2013-07-26 | 신상규 | Purification method of organic electroluminescent material |
| CN105315117A (en) * | 2014-07-15 | 2016-02-10 | 广东阿格蕾雅光电材料有限公司 | Novel purifying method of organic solid material |
| KR20160043888A (en) * | 2014-10-13 | 2016-04-22 | 한국생산기술연구원 | Method for purifing vapor-phase organic materials and Apparatus for purifing vapor-phase organic materials |
-
2017
- 2017-09-20 KR KR1020170121474A patent/KR102005471B1/en active IP Right Grant
-
2018
- 2018-06-19 CN CN201880004151.0A patent/CN109923689B/en active Active
- 2018-06-19 CN CN201910733354.XA patent/CN110473989B/en active Active
- 2018-06-19 WO PCT/KR2018/006919 patent/WO2019059499A1/en active Application Filing
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100852113B1 (en) * | 2006-11-08 | 2008-08-13 | 삼성에스디아이 주식회사 | Sublimation purification apparatus of organic light-emitting material and the material prepared by using the apparatus |
| CN102924207A (en) * | 2011-08-13 | 2013-02-13 | 广东阿格蕾雅光电材料有限公司 | Organic micromolecule sublimation purifying method |
| WO2013065626A1 (en) * | 2011-10-31 | 2013-05-10 | 出光興産株式会社 | Apparatus for purifying organic material and method for purifying organic material |
| KR20130076272A (en) * | 2011-12-28 | 2013-07-08 | 주식회사 두산 | Organic compound purifying apparatus |
| JP2013209352A (en) * | 2012-03-30 | 2013-10-10 | Idemitsu Kosan Co Ltd | Organic-material refining device |
| KR101288441B1 (en) * | 2013-02-20 | 2013-07-26 | 오강현 | Heater for sublimation refinement and method for forming the same |
| KR20160059609A (en) * | 2014-11-19 | 2016-05-27 | 덕산네오룩스 주식회사 | Display device using a composition for organic electronic element, and an organic electronic element thereof |
| CN106474760A (en) * | 2016-06-01 | 2017-03-08 | 陕西莱特迈思光电材料有限公司 | Organic matter sublimation purification device |
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| CN110473989B (en) | 2022-05-27 |
| WO2019059499A1 (en) | 2019-03-28 |
| KR102005471B1 (en) | 2019-07-30 |
| CN110473989A (en) | 2019-11-19 |
| KR20190032965A (en) | 2019-03-28 |
| CN109923689A (en) | 2019-06-21 |
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